Process for converting olefinic hydrocarbons to ketones



Patented Apr. 14, 1953 PROCE S -QB' CON T N L F IC j HYDRQQAlIiliQNS T KETONES Harri." dc V.-

Berkeley, d K n th E- Fnrman, Richmond, Calif assignors. to Shell. Development Company, Emeryville, Califi, a.

corporation of Delaware No Drawing. Application June 23, 1951,

Serial No. 234,151

h me ze -eh This invention relates to a process whereby olefinic hydrocarbons are reacted with Water in the presence of a catalyst to produce ketones having the same number of carbon. atoms as the olefinic eactan The rocesses hitherto employed in forming,

ketones from olefins in; this manner possess a number otdrawbacks. For one thing, their productivity has been low' since it has not been possible to obtain a. good conversion of olefin to hetone, per pass through the reactor, except as theieed stream is passed through the. catalyst at abnormally low rates. Again, the prior art proc: esses have. not been adapted for either liquid or gaseous phase operation, they having, in general, been. limited to vapor phase operations. Since ma of he igher efies; n fin e hydro..- carbons which desirablyare convertedtoketonesi e i id i eer e ne-man m loye in fecting the conversion, i-t would be desirable-if an efficient method were available which would permit of either vapor, liquid, or mixed vapor and liquid phase operations, and so. would be well adapted for use withall: types of olefinic hydrocarbon reactants.v

It is our discovery that olefinic hydrocarbons can be reacted with water to produce good yields of the. corresponding ketones when the reaction is conducted at elevated temperatures and pres,- sures in the presence of. at least one sulfide or molybdenum, tungsten, tellurium or selenium. In the preferred practice of the invention, there is also employed a quantity, not to exceed? about. 40 mole percent, based on the total amountiof catalyst employed, of a, sulfide of iron, cobalt or nickel, and a particularly desirable-catalyst com: bination has been found to be a mixtur'e'of tungsten sulfide and nickel sulfide. Use of anyof these catalysts r catalystcombinations ha'sibeen found to give high conversions of the olefinic reactants as well as high yields of the desired ketones even when the reactants, are passed through the catalyst. at relatively rapidrates',,. this being. particularly true', when the reaction is. conductedinthevaporphase;

The term .conversion is employed. herein to, designate the percentage of thefolefinic reactant whichis convertedto ketones and other reaction pfdducte le rem ld 'ri ie e prcentof the converted olefinic portion which goes toketones.

e l ile emeerbqes 9- e emplqyey as reactants are. those which contain. an aliphatic chain of. at least three carbon atoms, between two of which thereexists' an aliphatic double bond. They a be dim a d ariet of oun s nclud n h s f a o mal y seous nature as well as those which are liquids either at room temperatures or under the elevated pressure conditions which prevail during the reaction, Representativereactants, anyone or more. ot'which can be eonverteglto a ketone in accordance with the method. oi the. present invention, include. propylene, isopropylene, l-butene,v 2-1 1..- tene, 1 --pent,ene, 2-pentene, z methyl-2-butene, l-hexene, Z-hexene,v 3-henene, S rnethyl-L-pemtene, 3-methy1-2-pentne,I-heptene, Z-heptene, l-octene, 2-octene, 3.-ethyl-2hexene, l-nonene, Zmonene, 1-deoene, 2,7i-d-iinethy1-Z-octene, 2-. methyl-5-ethyl;-5 heptene,. l-dod'ecene, l-hexadecene, allyl benzene, propenyl benzene, 3-.phen.- yl-,lhexene, i-o-tolyl-ix-butene, and. 1,6 diphenyI-EmeXene. The ol'efins fvvhicl contain at least 5 carbonatomsv in. the molecule, as. 1-.- and Z-pentene, l hepteneland. 2o.c.ten'e,.and the. likepconstitute. a preferred reactant class. for em ployment inthe lpresent invention The aboveeinentioned and. other. olefinic compounds. can be, treated "individually, or when mixed with one. another orwithaliphatically sat.-. urated organic compounds, llhus, it is. possible. to employ olefin containing, mixtures which containetzen. less. thanf50.%, oi the: olefinic reactant,(s).as" is the. case with, by-product. streamsobtained from various petroleum refining. operationsl The latter streams, which normally cont in ie e ee f nd-Qt mief y e s. cane em yed:-ee-recev i d in the fiher and the presence ofthe large proportion. of; non-olefinic' diluent gases. in no wisedecreases the; eiiieiency of the present process-as regards eqi ver neml ds t oughh oup a given unit. is-naturallyimpaired when feed: streams low fi ia ree t nte e empl talystsused in the;process-of;v the present; i rrven. ion are solidswhich can be preparedby any of. the metlodsv knowmin the. art. Further, he e m yee. an w W rm. as. granules, pellets, powders oig-thellhe, and theyee: see-heme nialas pumice, in

"the

nt ne the, la ms re et nt combines with the water in equimolar proportions, with the resulting product then yielding up hydrogen to form the ketone. However, while equimolar reactant proportions can be used with success, the preferred practice is to employ an excess of water. Particularly good results have been obtained by employing from about 2 to moles of water for each mole of olefinic compound.

As noted above, the reaction between the olefinic compound and water goes forward in the presence of the sulfide catalyst at elevated temperatures and pressures. As regards the temperature, a suitable range is from about 200 to 500 (3., though a preferred range is from about 250 to 400 C. Pressures of from about 150 to 2000 p. s. i. have been employed with good results, though somewhat lower or even higher pressures can be used upon occasion.

The reaction can be effected either batchwise, intermittently or continuously. Thus, in batch operations the reactants, in either gaseous or liquid form, maybe placed, together with the catalyst, in a suitable pressure vessel and allowed to remain there under the desired reaction conditions for a suitable reaction interval, the latter normally varying from to or more hours, depending on the degree of reaction completeness sought. The longer intervals favor a more extensive conversion of the olefinic materials present in the feed. In continuous methods of operation, the reactants, in the desired physical state, are passed through a body of the catalyst supported within a reactor vessel. When operating in this fashion it is preferred to main- H tain the reactants in the vaporous state since higher throughput rates can then be employed, while still obtaining good olefin conversion and ketone yields. Thus, the activity of the sulfide catalysts described above is such as to permit of obtaining good results even when employing space velocities in excess of 800, the term space velocity being employed herein to designate the grams of hydrocarbon in the feed stream which are contacted with a liter of catalyst, per hour. In general, when operating in the vapor phase it is preferable to practice the process of this invention at space velocities of at least 200.

The ketones produced by the present process can be recovered from the reacted mixture in any desired manner, as by distillation, or by extraction with water, followed'by distillation. In vapor phase operations, the unreacted gases, or at least the olefinic portion thereof, are preferably recycled back through the reactor along with new quantities of the feed gases in order to obtain maximum olefin conversion.

The sulfide catalysts employed in the present process are characterized by an unusually long, active life. However, when it appears that the activity of the catalyst has fallen oil to any appreciable extent, the catalyst may be restored to its original level of activity by burning with an oxygen-containing gas, and preferably by passing a stream of sulfur dioxide (admixed with an inert diluent gas) through the catalyst bed for a short time. This regeneration can be effected in situ at the reaction temperatures employed in the reaction, thus eliminating temperature adjustments in the bed.

In the following examples, which illustrate the process of the invention in various of its embodi-' ments, the tungsten sulfide-nickel sulfide catalyst employed, which contained about 2 moles nickel and 4 moles sulfur per mole of tungsten,

4 was prepared by dissolving tungstic acid in aqueous ammonia to form a solution of ammonium tungstate. Hydrogen sulfide was then passed into the solution to convert the tungstate to the corresponding thiotungstate. A second solution containing the required amount of soluble nickel salt was then added to the thiotungstate solution, thereby precipitating the nickel 'sulfide. The tungsten was then precipitated (largely as tungsten trisulfide) by adding an acid, e. g., 25% sulfuric acid, until the pH of the solution was reduced to a value between about 1 and 2. The precipitated sulfide mixture was then separated from the solution and dried in an atmosphere of hydrogen sulfide. In the liquid phase experiments, the catalyst was charged as a powder, while in the vapor phase runs, the catalyst was pelleted and then pre-treated with hydrogen at 300 C.

The molybdenum sulfide catalyst employed was made up of molybdenum trisulfide. It was catalyst No. Mo-40'7, a product of The I-Iarshaw Chemical Company, obtained and used in tablet form.

EXAMPLE I In this operation, a vaporous mixture of olefin and water was passed through a heated, steel reaction tube containing the above-described tungsten sulfide-nickel sulfide catalyst. The hydrocarbon and water were pumped separately to a pre-heating unit which vaporized the reactants, with the vaporous mixture then being fed under pressure through the reaction chamber wherein the reaction temperature was maintained at the desired level by an electrical heating unit. The efiluent from the tube was condensed in a water-cooled condenser-receiver to provide a liquid from which the Water layer was separated. The oil layer was fractionated, yielding a hydrocarbon fraction, a ketone fraction and a higher boiling fraction. Table I given below shows the results obtained by using various olefinic reactants and different reaction conditions.

TABLE I Vapor phase conversion of olefin to ketone over tungsten sulfide-nickel sulfide catalyst at a pressure of 500 p. s. i. and temperature of 1 Obtained by dimerization of propylene. Obtained by cracking of paraffin Wax.

EXAMPLE II In this operation, l-octene was reacted with water in the liquid phase over a variety of catalysts, as shown in Table II below. These operations were carried out in a 300 ml. stainless steel hydrogenation-type bomb fitted to a rocking type or heater. The reactants were heated with agitation for the desired period of time, and under the elevated pressure condition (about 1600 p. s. 1.) developed on heating the enclosed contents of the bomb to 300 C. After cooling, the products were removed and the (powdered) catalyst filtered off. The ketonic portion of the resultant liquid was recovered by the method described in Example I above.

TABLE II prising at least one compound selected from the group consisting of the sulfides of molybdenum,

tungsten, tellurium and selenium, together with Charge Olefin Time, Conver- Ktone Run No. Catalyst t C t 1 t hrs sion l2Z1eld,t

l-oc ene water a a ys ercen moles moles g. Percent 0.4 1.0 so 12 s5 38 0.4 5.5 12 51 3a 0.4 5.5 10 4 33 26 0.41 5.5 10 1 27 13 0.41 5.5 1 12 21 0.39 5.5 10 12 60 21 The invention claimed is: 20 a total of from about 0 to 40 mole percent, in

1. The process for converting anolefinic hydrocarbon'containing an aliphatic chain of at least 3 carbon atoms, between two of which there exists aliphatic double bond, to a ketone having the same number of carbon atoms as the hydrocarbon, which comprises treating said hydrocarbon with water at a temperature between about 200 and 500 C. at a pressure of from about 150 to 2000 p. s. i. in the presence of a catalyst comprising at least one compound selected from the group consisting of the sulfides of molybdenum, tungsten, tellurium and selenium, together with a total of from about 0 to 40 mole percent, in terms of the total catalyst composition, of at least one other catalyst selected from the group consisting of the sulfides of nickel, iron and cobalt.

2. The process of claim 1 wherein the catalyst comprises a mixture of tungsten sulfide and nickel sulfide.

3. The process of claim 1 wherein the catalyst comprises molybdenum trisulfide.

4. The process for converting an olefinic hydrocarbon containing an aliphatic chain of at least 3 carbon atoms, between two of which there exists an aliphatic double bond, to a ketone having the same number of carbon atoms as the hydrocarbon by treatment with water, which comprises passing a vaporous mixture containing from about 2 to 10 moles of water per mole of said hydrocarbon, at a temperature between about 200 and 500 C. and at a pressure of from about 150 to 2000 p. s. 1., through a catalyst comterms of the total catalyst composition, of at least one other catalyst selected from the group consisting of the sulfides of nickel, iron and cobalt.

5. The process of claim 4 wherein the hydrocarbon'reactant comprises an olefin containing at least 5 carbon atoms. 6. The process of claim 4 wherein the hydrocarbon reactant comprises an olefin containing at least 5 carbon atoms, and the catalyst comprises a mixture of tungsten sulfide and nickel sulfide.

7. The process for converting an olefin containing at least 5 carbon atoms to a ketone having the same number of carbon atoms as the olefin, which comprises treating said olefin with water at a temperature between about 250 and. 400 C.'and at a pressure between and 2000 p. s. i. in the presence of a catalyst comprising a mixture of tungsten sulfide and nickel sulfide.

8. The process of claim 7 wherein the olefin is l-octene.

HARRY DE V. FINCH. KENNETH E. FURMAN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,999,620 Van Peski Apr. 30, 1935 2,162,913 Eversole et a1 June 20, 1939 2,414,951 Jasaitis et al Jan. 28, 1947 2,523,686 Engel Sept. 26, 1950 

1. THE PROCESS FOR CONVERTING AN OLEFINIC HYDROCARBON CONTAINING AN ALIPHATIC CHAIN OF AT LEAST 3 CARBON ATOMS, BETWEEN TWO OF WHICH THERE EXISTS ALIPHATIC DOUBLE BOND, TO A KETONE HAVING THE SAME NUMBER OF CARBON ATOMS AS THE HYDROCARBON, WHICH COMPRISES TREATING SAID HYDROCARBON WITH WATER AT A TEMPERATURE BETWEEN ABOUT 200 AND 500* C. AT A PRESSURE OF FROM ABOUT 150 TO 2000 P.S.I. IN THE PRESENCE OF A CATALYST COMPRISING AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE SULFIDES OF MOLYBDENUM, TUNGSTEN, TELLURIUM AND SELENIUM, TOGETHER WITH A TOTAL OF FROM ABOUT 0 TO 40 MOLE PERCENT, IN TERMS OF THE TOTAL CATALYST COMPOSTION, OF AT LEAST ONE OTHER CATALYST SELECTED FROM THE GROUP CONSISTING OF THE SULFIDES OF NICKEL, IRON AND COBALT. 